WO2023179036A1 - Oxyde composite, procédé de préparation d'oxyde composite, catalyseur d'hydrogénation et son utilisation - Google Patents

Oxyde composite, procédé de préparation d'oxyde composite, catalyseur d'hydrogénation et son utilisation Download PDF

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WO2023179036A1
WO2023179036A1 PCT/CN2022/129813 CN2022129813W WO2023179036A1 WO 2023179036 A1 WO2023179036 A1 WO 2023179036A1 CN 2022129813 W CN2022129813 W CN 2022129813W WO 2023179036 A1 WO2023179036 A1 WO 2023179036A1
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composite oxide
solution
titanium dioxide
catalyst
range
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Chinese (zh)
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杜周
刘艳惠
张富春
刘宗语
季静
任玉梅
杨光
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中国石油化工股份有限公司
中石化(北京)化工研究院有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • the invention relates to a composite oxide, a preparation method of the composite oxide, a hydrogenation catalyst and its application. Specifically, it can be used to hydrogenate and remove alkynes in the C 4 fraction and increase the production of butadiene.
  • C4 fraction refers to a mixture of various alkanes, olefins, diolefins and alkynes containing four carbon atoms. It is mainly derived from the refinery gas produced in the petroleum refining process and the by-product of the cracking of petroleum hydrocarbons to ethylene.
  • Cracking C4 contains n-butane, isobutane, 1-butene, trans-2-butene, cis-2-butene, isobutene, 1,2-butadiene, 1,3-butadiene, methyl Saturated hydrocarbons and unsaturated hydrocarbons such as ethyl acetylene, ethyl acetylene and vinyl acetylene are mainly used in industry to produce 1,3-butadiene, isobutylene and 1-butene.
  • the cracked carbon four fraction a by-product of high-temperature cracking of hydrocarbons to produce ethylene, usually contains 40%-60% mass fraction of butadiene.
  • Butadiene is an important monomer in the synthetic rubber industry.
  • Butadiene is extracted from the cracked carbon four fraction.
  • Solvent extraction methods are usually used, such as acetonitrile method, N-methylpyrrolidone method and dimethylformamide method. At present, these methods basically meet the requirements for butadiene purity.
  • alkynes in mixed carbon tetrahydrocarbon fractions can be removed by catalytic selective hydrogenation.
  • the catalysts used mainly tend to use precious metal catalysts represented by palladium, platinum, silver, etc., followed by non-noble metal catalysts represented by copper and nickel.
  • the selective hydrogenation of alkynes in hydrocarbon streams depends on the composition of the raw materials and the target products, and the catalysts and reaction conditions selected are also different.
  • a good selective hydrogenation catalyst should also have good stability, that is, the catalyst must have the ability to resist impurities and colloids, so as to extend the life of the catalyst. Therefore, the carrier is required to have lower acidity, smaller specific surface area and larger pore size.
  • adding some additives during the preparation of the catalyst can also extend the service life of the catalyst.
  • Precious metal catalysts generally use palladium catalysts supported on carriers (usually alumina), and add other cocatalyst components, such as gold, silver, chromium, copper, iron, rhodium, lithium, potassium, and lead or zinc.
  • Precious metal catalysts have good low-temperature activity and mild reaction conditions.
  • their shortcomings are that the active components of the catalyst are easy to lose, are expensive, are not easy to regenerate, and have slightly poor hydrogenation selectivity.
  • Non-noble metal catalysts need to react at higher temperatures, and the hydrogenation conditions are more stringent. However, they are simple to prepare, easy to regenerate repeatedly, and the cost is relatively low, so they still have certain research and development value.
  • the semi-hydrogenated free radicals adsorbed on the catalyst react with adjacent alkynes or dienes to form a viscous polymer (commonly known as green oil), which is mainly composed of C 6 and above
  • green oil which is mainly composed of C 6 and above
  • the compound composition covers the surface of the catalyst and blocks the micropores on the surface of the catalyst, reducing the activity of the catalyst and affecting the service life of the catalyst.
  • conjugated dienes such as 1,3-butadiene
  • the polymerization reaction proceeds more easily, thereby deactivating the catalyst in a short time, so that the catalyst must be regenerated frequently before it can be reused.
  • the structure and shape of catalytic materials based on TiO 2 can greatly affect the light absorption efficiency of the material.
  • Coral reefs have excellent light-absorbing and reflective structures, thus providing a three-dimensional (3D) environment for many plants and animals on the seafloor, absorbing small particles and supporting approximately a quarter of all known marine life.
  • Coral-like 3D hierarchical structures can have higher specific surface areas, resulting in more active sites and stronger light-harvesting capabilities, and have been shown to have better photocatalytic performance than other structures.
  • the performance of TiO2- supported catalysts can be improved by using specific catalytic materials with a coral reef-like morphology.
  • the purpose of the present invention is to provide a non-noble metal selective hydrogenation catalyst with high low-temperature activity, high selectivity and high stability. Compared with precious metal selective hydrogenation and alkyne removal catalysts, the catalyst investment cost of the present disclosure can be saved by more than 80%, and the catalyst has better resistance to impurity poisoning and raw material adaptability.
  • the present invention provides a composite oxide, which includes aluminum oxide and titanium dioxide, the specific surface area of the composite oxide is expressed as X m 2 /g, and the average pore diameter of the composite oxide is expressed as Y nm , wherein the ratio of Preferably, the ratio of X to Y is 5 to 15. Further preferably, the ratio of X to Y is 5 to 10.
  • titanium dioxide in the anatase crystal phase accounts for 96wt%-100wt% of the total titanium dioxide.
  • titanium dioxide in the anatase crystal phase accounts for 97wt%-100wt% of the total titanium dioxide.
  • titanium dioxide in the anatase crystal phase accounts for 98wt%-100wt% of the total titanium dioxide.
  • titanium dioxide in the anatase crystal phase accounts for 99wt%-100wt% of the total titanium dioxide.
  • the proportion of titanium dioxide in the anatase crystal phase to the total titanium dioxide can be measured through X-ray diffraction analysis.
  • the specific surface area of the composite oxide can be measured by the BET method.
  • the average pore size of the composite oxide can be measured by the nitrogen adsorption isotherm curve method.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 95 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 96 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 97 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the diffraction peak area representing the crystal structure of anatase titanium dioxide, measured by X-ray diffraction analysis accounts for 98 wt % to 100 wt % of the diffraction peak areas of all titanium dioxide crystal structures.
  • the pore volume of the composite oxide measured using the P/Po single-point desorption curve is Z mL/g, and the ratio of X to Z is 220 to 400, preferably 250 to 350. In some embodiments, the ratio of
  • X is from 90 to 150. In some embodiments, X is 90, 100, 110, 120, 130, 140, 150, or a range consisting of any two thereof.
  • Y is from 9 to 20, preferably from 12 to 16. In some embodiments, Y is 12, 13, 14, 15, 16, or a range consisting of any two thereof.
  • the proportion of pores with pore diameters in the range of 10-20 nm to all pores is at least 85% by volume.
  • Z is from 0.3 to 0.5, preferably from 0.3 to 0.4. In some embodiments, Z is 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, or a range consisting of any two thereof.
  • the composite oxide contains 5 wt% to 21 wt% titanium dioxide, based on the total weight of the composite oxide. In some embodiments, the composite oxide contains 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 21wt% or within the range of any two of them. Titanium dioxide.
  • the composite oxide contains 79 wt% to 95 wt% aluminum oxide, based on the total weight of the composite oxide.
  • the composite oxide has a coral plexus-like 3D layered structure.
  • the 3D hierarchical structure of coral clusters can have a higher specific surface area, resulting in more active sites and stronger light-harvesting capabilities.
  • the present invention provides a method for preparing a composite oxide, through which an alumina-titanium dioxide composite oxide with a 3D microscopic morphology of coral clusters can be obtained.
  • the preparation method of the present invention includes the following steps:
  • Step 1 Dissolve the soluble aluminum source in water to form an aluminum source solution, dissolve the titanium source in an acid solution to form a titanium source solution, and mix ammonium salt and alkali solution to form a mixed alkali solution;
  • Step II (a) Add the titanium source solution and the mixed alkali solution to the aluminum source solution, so that the resulting mixed solution maintains the first pH value for a first period of time; (b) Add the titanium source solution and the mixed alkali solution to the mixed solution Adding additional mixed alkali solution to maintain the resulting mixed solution at a second pH value for a second period of time; (c) adding additional titanium source solution to the mixed solution to maintain the resulting mixed solution at a third pH value for a second period of time; Three time periods;
  • Step III After step II.(c), increase the temperature of the mixed liquid and maintain it for a fourth period of time to obtain a precipitate;
  • Step IV The precipitate is dried and roasted to obtain a composite oxide containing alumina and titanium dioxide.
  • the precipitate is also washed and filtered (to remove unnecessary impurities) before drying.
  • the composite oxide thus obtained has the composition and structural characteristics described in the first aspect of the invention.
  • the first pH value is less than 5, preferably between 3 and 4.
  • the second pH value is greater than 8.5, preferably between 9 and 10.
  • the third pH value is greater than 7 and less than 9, preferably 7.5 to 8.5.
  • the first time period, the second time period and the third time period are respectively 5 minutes to 20 minutes, preferably 10 minutes to 15 minutes.
  • the fourth time period is from 20 minutes to 60 minutes.
  • the operating temperature is from 25°C to 60°C, preferably from 50°C to 60°C.
  • the temperature in said step III, is increased to 80°C to 150°C, preferably 80°C to 100°C. In some embodiments, in step III, the temperature is increased to 80°C, 85°C, 90°C, 92°C, or 95°C.
  • the drying temperature is 110°C to 130°C. Drying time is 4-12h, preferably 6-10h
  • the calcination temperature is 800°C to 1000°C. In some embodiments, in step IV, the calcination temperature is in the range of 800°C, 850°C, 900°C, 950°C, or any two thereof.
  • the roasting time is 4-12h, preferably 5-8h
  • the aluminum source solution has an aluminum concentration of 0.5 to 2.5 mol/L.
  • the aluminum source is a soluble aluminum salt, and one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, and organic aluminum such as aluminum isopropoxide, aluminum sec-butoxide, aluminum monoacetate, and aluminum diacetate can be selected. kind.
  • the titanium concentration of the titanium source solution is 0.2 to 1.2moL/L.
  • the titanium source is a soluble titanium source, which can be selected from titanium salts such as titanium acetate, hydrochloride, sulfate, nitrate or titanate esters such as tetraethyl titanate and tetra-n-propyl titanate. , tetraisopropyl titanate and tetrabutyl titanate.
  • the ammonium salt concentration of the mixed alkali solution is 0.1 to 0.3moL/L.
  • the ammonium salt may be selected from one or more types of ammonium bicarbonate, ammonium carbonate, and organic ammonium salts.
  • the alkali concentration is 0.2 to 0.4moL/L.
  • the alkali solution can be selected from ammonia, sodium hydroxide, potassium hydroxide and organic bases such as triethylamine, N,N-2 toluidine, pyridine and quinoline.
  • the acid solution can be one or more selected from sulfuric acid, nitric acid, hydrochloric acid, and organic acids such as formic acid, acetic acid, citric acid, and oxalic acid.
  • the reactant input ratios in steps II(a), II(b) and II(c) are as follows:
  • the titanium source solution charging ratio in steps II(a) and II(c) can be 1:4-2:3.
  • the feeding amount of the titanium source solution in step II(a) accounts for 20%-40% of the total titanium source solution feeding volume in the method
  • the feeding amount in step II(c) accounts for 20%-40% of the total titanium source solution feeding volume in the method. 60%-80% of the total titanium source solution feeding volume
  • the feeding ratio of the mixed alkali solution in steps II(a) and II(b) can be in the range of 2:1 to 1:2, or in the range of 1.5:1 to 1:1.
  • the input amount of the mixed alkali solution in step II(a) accounts for 33%-67%, preferably 50%-60%
  • the input amount in step II(b) accounts for 33%-670%, preferably 40%-50% , relative to the total feed volume in II(a) and II(b).
  • the precipitate washing process includes washing with deionized water until acid ions cannot be detected, the drying temperature is 100°C to 120°C, and the drying time is 4°C to 12h, The calcination temperature is 800°C to 1000°C.
  • the composite oxide prepared by the method provided by the present invention contains 5wt% to 21wt% titanium dioxide, and the titanium dioxide and alumina are uniformly mixed. And the inventor was surprised to find that the surface microstructure of the composite oxide showed a 3D layered structure of coral clusters.
  • the coral-like 3D layered structure can make the composite oxide have a higher specific surface area, thereby having more active sites and stronger electron capture ability, which helps to promote the catalytic effect of TiO 2 as an electron promoter, Thereby improving the overall performance of the catalyst such as activity and selectivity.
  • the roasting temperature of TiO 2 starts to produce rutile from 500°C, and most of the crystal phase of TiO 2 above 700°C changes from anatase phase to rutile phase.
  • the composite oxide prepared by the method provided by the present invention is roasted at a high temperature of 800°C or higher, it is found through X-ray diffraction analysis that anatase titanium dioxide accounts for 95wt%-100wt% of all crystal phases of TiO2 . Breaks common sense.
  • TiO 2 existing in the form of anatase in the composite oxide has an electron induction effect and can effectively induce a decrease in the electron cloud density of the active metal Ni in the prepared catalyst (compared to the rutile phase generated by high-temperature roasting), thus Enhance the adsorption capacity of alkynes in the reaction raw materials and improve the selective hydrogenation activity and selectivity of the catalyst.
  • the present invention also provides an application of a composite oxide, which includes the use of the composite oxide prepared according to the first aspect of the present invention or the composite oxide prepared by the method of the second aspect as a catalyst carrier.
  • the type of catalyst is not particularly limited.
  • the present invention provides a hydrogenation catalyst, which includes a composite oxide according to the first aspect of the present invention or a composite oxide prepared according to the method according to the second aspect, and an active component, such as Palladium, nickel, iron or cobalt.
  • the hydrogenation metal is nickel.
  • the hydrogenation catalyst may have a nickel content of 8-25 wt%, preferably 12-20 wt%.
  • the hydrogenation catalyst includes palladium, which may be present in an amount of 0.1-2 wt%, such as 0.15-1.5 wt%.
  • the present invention also provides an alkyne selective hydrogenation method, which hydrogenation method includes performing alkyne selective hydrogenation on distillate oil in the presence of the hydrogenation catalyst described in the third aspect to increase the production of butylene.
  • Alkene wherein the distillate oil includes C4 distillate oil, preferably the high-alkyne tail gas produced by a butadiene extraction unit.
  • the reaction temperature is 20°C to 40°C
  • the molar ratio of hydrogen to alkyne is 1:1 to 2.5:1
  • the pressure is 0.5MPa to 0.8MPa
  • the circulation ratio is 10 :1 to 30:1.
  • the catalyst provided by the invention exhibits high vinyl acetylene conversion rate and high 1,3-butadiene selectivity in the selective hydrogenation of alkynes.
  • Figure 1 shows the 3D microscopic morphology of the coral cluster of the alumina-titanium dioxide composite oxide prepared in Example 1.
  • Figure 2 shows the XRD pattern of the alumina-titanium dioxide composite oxide prepared in Example 1.
  • the raw materials or components used in the present invention can be prepared through commercial channels or conventional methods.
  • the ASAP ⁇ 2020 adsorption instrument (N 2 adsorption and desorption method) of the American Mike Instrument Company was used to determine the specific surface area and pore structure of the composite oxide. Before testing, the composite oxide sample was degassed at 623K for 4 hours, and nitrogen was adsorbed at liquid nitrogen temperature. AMSM software was used to process the sample data, and the Brunauer-Emmet-Teller (BET) method was used to obtain the specific surface area of the sample. The Barrett-Joyner-Halenda (BJH) method was used to obtain the average pore diameter based on the nitrogen adsorption isotherm curve, and the P/Po single-point desorption curve was used to obtain the pore volume.
  • BET Brunauer-Emmet-Teller
  • BJH Barrett-Joyner-Halenda
  • the morphology of the composite oxide was observed using FEI's QUANTA 200 scanning electron microscope.
  • the crystal phase structure of the composite oxide was characterized using an EMPYREAN X-ray diffractometer from PANalytical Corporation of the Netherlands.
  • Cu K ⁇ is the radiation source X-ray tube voltage 40kV, light tube current 40mA, slit width 10mm, scanning range: 5-90°, scanning speed: 0.013°/s.
  • the temperature was raised to 92°C, maintained for 20 minutes, filtered, and the filter cake was repeatedly washed 5 times with 20 times the volume of deionized water.
  • the washed filter cake was dried at 110°C for 6 hours and roasted at 850°C for 5 hours. 114.3g of composite oxide with a TiO2 content of 15.0wt% was obtained.
  • FIG. 1 shows the surface micromorphology of the composite oxide exhibits a 3D layered structure of coral clusters.
  • Figure 2 shows the XRD pattern of the alumina-titanium dioxide composite oxide prepared in Example 1.
  • Dissolve 32.15g Ti(SO 4 ) 2 in deionized water add 5 mL (98%) concentrated sulfuric acid, and prepare 500 mL of dilute sulfuric acid solution of titanium sulfate.
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 379.79g Al(NO 3) 3 is dissolved in deionized water to prepare 1000 mL of aluminum nitrate solution. Dissolve 25.99g Ti(OCH 3 CH 2 ) 4 in absolute ethanol to prepare 500 mL of tetraethyl titanate ethanol solution. Finally, 9.1% alumina-titanium dioxide composite oxide was obtained.
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 396.92g Al(NO 3 ) 3 is dissolved in deionized water to prepare 1000 mL of aluminum nitrate solution. Dissolve 6.13g TiO(OH) 2 in the sulfuric acid solution, add deionized water, and prepare 500 mL of dilute sulfuric acid solution of metatitanic acid. Finally, 5.0% alumina-titanium dioxide composite oxide was obtained.
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 396.92g Al(NO 3 ) 3 is dissolved in deionized water to prepare 1000 mL of aluminum nitrate solution. Dissolve 6.13g TiO(OH) 2 in the sulfuric acid solution, add deionized water, and prepare 500 mL of dilute sulfuric acid solution of metatitanic acid. The filter cake baking temperature is changed to 800°C, and finally 5.0% alumina-titanium dioxide composite oxide is obtained. .
  • Example 2 Repeat the preparation process of the titanium dioxide-alumina composite oxide in Example 1, except that 374.13g AlCl3 ⁇ 6H 2 O is dissolved in deionized water to prepare 1000 mL of aluminum chloride solution. Dissolve 59.99g Ti(OCH 3 CH 2 ) 4 in absolute ethanol to prepare 500 mL of tetraethyl titanate ethanol solution. Finally, 21.0% alumina-titanium dioxide composite oxide was obtained.
  • Dissolve 24.5g TiO(OH) 2 in the sulfuric acid solution add deionized water to prepare 1000 mL of dilute sulfuric acid solution of metatitanic acid.
  • Control the flow rate of the mixed alkali solution to keep the pH value of the precipitate in the range of 5.0-6.0 for 8 minutes then increase the flow rate of the mixed alkali solution to keep the pH value of the mixed solution in the range of 8.5-9.5 for 8 minutes, and then Reduce the flow rate of the mixed alkali solution to keep the pH value of the mixed solution in the range of 5.0-6.0 for 8 minutes, then increase the flow rate of the mixed alkali solution to keep the pH value of the precipitate in the range of 8.5-9.5, and repeat this until the solution A1 and B1 are all added dropwise.
  • solution A1 Take 401.88g of analytically pure AlCl 3 ⁇ 6H 2 O and dissolve it in 1000ml of deionized water to prepare solution A1; take 43.25g of chemically pure Ti(OCH 2 CH 3 ) 4 and dissolve it in 500ml of benzene (benzene content is 99.8 (Wt )%), prepare solution B1; take 18g of analytically pure NH 4 HCO 3 , dissolve it in 600 ml of deionized water, add 250 ml of ammonia water with a concentration of 24-28 wt%, stir and mix evenly, and then add deionized water to prepare 1000 ml of solution C1.
  • the N2 adsorption-desorption method was used to determine the specific surface area and pore structure of the composite oxide on the carrier prepared above.
  • Example 4 90% Example 5 85% Example 6 85% Comparative example 1 78% Comparative example 2 34% Comparative example 3 82%
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100 mL of 12.24 g Ni/100 mL of nickel nitrate aqueous solution to impregnate 100 g of the above-mentioned calcined catalyst precursor.
  • the impregnation time is 0.5 h. After drying, it is dried at 110°C for 4 hours and roasted at 550°C for 6 hours to obtain a Ni content of 19.82%. Ni/Al 2 O 3 -TiO 2 Catalyst B.
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100mL of 20gNi/100mL nickel nitrate aqueous solution to impregnate 100g of the above-mentioned calcined catalyst precursor. The impregnation time is 0.5h. After drying, it is dried at 110°C for 4h and roasted at 550°C for 6h to obtain a Ni content of 25% Ni/ Al 2 O 3 -TiO 2 Catalyst D.
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100 mL of 12.24 g Ni/100 mL of nickel nitrate aqueous solution to impregnate 100 g of the above-mentioned calcined catalyst precursor.
  • the impregnation time is 0.5 h. After drying, it is dried at 110°C for 4 hours and roasted at 550°C for 6 hours to obtain a Ni content of 19.82%. Ni/Al 2 O 3 -TiO 2 Catalyst E.
  • the impregnation time is 0.5 h. After filtering, drying at 110°C for 5 h and roasting at 550°C for 5 h. Then use 100 mL of 12.24 g Ni/100 mL of nickel nitrate aqueous solution to impregnate 100 g of the above-mentioned calcined catalyst precursor. The impregnation time is 0.5 h. After drying, it is dried at 110°C for 4 hours and roasted at 550°C for 6 hours to obtain a Ni content of 19.82%. Ni/Al 2 O 3 -TiO 2 Catalyst F.
  • Example 1 Immerse 100g of the composite oxide prepared in Example 1 into 85mL of a palladium chloride aqueous solution with a palladium atom content of 0.32g/100mL, take it out after 1.5 hours, filter out the impregnated composite carrier, and use 120mL of a palladium chloride solution with a concentration of 10wt%.
  • the hydrazine hydrate aqueous solution is reduced at room temperature for 1 hour, rinsed repeatedly with deionized water until the chloride ions are washed away, drained and dried at 120°C for 6 hours, and then roasted at 480°C for 4 hours to obtain a palladium content of A Pd/Al 2 O 3 -TiO 2 catalyst H with a Pd content of 0.3% was obtained.
  • This example is the application of the catalyst in the selective hydrogenation reaction of butadiene extraction tail gas.
  • the catalysts used in this example are catalysts A-K.
  • the raw material used in this example is butadiene extraction tail gas from a certain plant.
  • the composition is shown in Table 3.
  • the fixed-bed small-scale evaluation device of Tuochuan Scientific Research Equipment Co., Ltd. is used, and 50 mL of catalyst is loaded to perform selective hydrogenation reaction of butadiene extraction tail gas.
  • reaction pressure is 0.5 to 0.7MPa
  • hydrogen volume is 1.92L/h
  • reactor inlet temperature is 25°C
  • circulation ratio is 20:1
  • raw material feed volume is 25mL/h.
  • Catalysts A to K were evaluated under the same conditions, and the results of hydrogenation and acetylene removal are shown in Table 4.
  • the catalyst provided by the present invention exhibits a high conversion rate of vinyl acetylene and a high selectivity of 1,3-butadiene. Because the vinyl acetylene in the hydrogenated product can be controlled within a lower range, the hydrogenated product can be directly returned to the extraction system to increase butadiene production.
  • Example 7 Catalyst A prepared in Example 7 was used to conduct a long-term stability experiment under the same conditions as in Example 15.
  • the stability evaluation experimental data for 1000 hours is as follows in Table 5:
  • the catalyst provided by the present invention exhibits high stability for the selective hydrogenation reaction of butadiene tail gas feedstock with high acetylene content.
  • the hydrogenation catalyst of the present invention not only has high 1,3-butadiene selectivity (%) and vinyl acetylene conversion rate (%), but also can be maintained at a high level for a long time, so it is suitable for long-term operation.

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Abstract

La présente invention concerne un oxyde composite, l'oxyde composite comprenant de 60 à 95 % en poids d'oxyde d'aluminium et de 5 à 40 % en poids de dioxyde de titane. La surface spécifique de l'oxyde composite déterminée au moyen d'un procédé BET est exprimée par X m2/g ; le diamètre de pore moyen de l'oxyde composite déterminé au moyen d'un procédé de courbe isotherme d'adsorption d'azote est exprimé en tant que Y nm, le rapport de X à Y étant de 5 à 30 ; et au moyen de la détermination du procédé de diffraction des rayons X, le dioxyde de titane dans une phase cristalline anatase dans l'oxyde composite représente 95 à 100 % en poids du dioxyde de titane total, X se situant dans la plage de 50 à 200, de préférence X se situant dans la plage de 60 à 180, de préférence dans la plage de 80 à 150, et Y se situant dans la plage de 5 à 25 nm. La présente invention concerne en outre un catalyseur d'hydrogénation comprenant l'oxyde composite, lequel catalyseur présente un taux de conversion d'acétylène de vinyle très élevé et une sélectivité de 1,3-butadiène élevée.
PCT/CN2022/129813 2022-03-24 2022-11-04 Oxyde composite, procédé de préparation d'oxyde composite, catalyseur d'hydrogénation et son utilisation WO2023179036A1 (fr)

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CN102886262A (zh) * 2011-07-21 2013-01-23 北京石油化工学院 C4炔烃选择加氢催化剂、制备方法及其应用
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CN113828289A (zh) * 2020-06-23 2021-12-24 中国石油化工股份有限公司 一种复合氧化物载体以及加氢精制催化剂及其制备方法和应用

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US20020183578A1 (en) * 1999-12-24 2002-12-05 Institut Francais Du Petrole Process for selective production of propylene from hydrocarbon fractions with four carbon atoms
US20020165092A1 (en) * 2000-12-29 2002-11-07 Qianwen Zhang Catalyst for selective hydrogenation, its preparation process and application
CN101172226A (zh) * 2006-11-01 2008-05-07 中国石油化工股份有限公司 一种超细钛铝复合氧化物及其制备方法
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